Note: Descriptions are shown in the official language in which they were submitted.
yL~,~4~
1104309
CARPET-TREATING COMPOSITIONS
The present invention relates to antistatic
agents useful in combination with soil-resistant carpet
treating compositions. More specifically, this invention
relates to antistatic agents which comprise certain alkyl
sulfate quaternary salts of N,N-bis(hydroxyethyl) amines.
The use of these antistatic agents with conventional
fluorochemical-containing carpet-treating compositions
provides synthetic fiber pile carpets with an improved
balance of soiling, static and aesthetic properties.
The use of synthetic fibers in the manufacture of
carpeting materials has created a problem in that carpets
having synthetic pile-fibers tend to induce the build-up of
electrostatic charge on a person walking on the carpet,
particularly at low relative humidities. The discharge of
the static electricity to ground, such as when the charged
person touches a doorknob, light switch, or another person
is annoying and can be painful. Synthetic pile carpets also
exhibit increased receptivity to soiling and must be
treated to improve their soil resistance and cleanability.
Recently carpet manufacturers have employed low
denier synthetic organic fibers, such as nylon, to provide
carpets having a very soft "hand." Treatment of these
carpets w~th the known soil-resistant, antistatic, carpet-
treating compositions may not be satisfactory since the
balance between performance characteristics of the carpet,
e.g. hand (softness), luster, static propensity and soiling
characteristics, may not be maintained. In particular, an
improvement in one property, for examp]e static propensity,
may be obtained at the expense of another extremely
important property such as hand. Recently several soil and
-- 1 -- ~
30~
staln-resistant treat}nents for carpets have been developed
which are based on specific fluoroaliphatic radical-
containing compositions. Exemplary treating compositions
and processes are known which decrease the static propen-
sity of carpets. As described hereinafter, they have notproven to be satisfactory due to the accompanying
deleterious effects on other performance properties such
as hand or luster.
The present invention provides means by which
the static propensity of synthetic fiber pile carpets,
particularly low denier, e.g. 6 denier, nylon pile carpets
is decreased, while substantially maintaining other
performance properties such as hand, luster and soil
resistance. More specifically, the present învention
provides antistatic agents which can be used in combina-
tion with conventional fluorochemical containing carpet-
treating compositions to provide coatings for synthetic
carpet fibers which have significantly reduced static
propensity while substantially maintaining other carpet
performance properties. The antistatic agent can be
applied as a separate treatment in combination with the
conventional soil-resistant treatment or coapplied with
the conventional treatment, i.e. as an additive to the
conventional treating compositions.
The antistatic agents of the present invention
comprise salt molecules which are certain dialkyl sulfate
quaternary salts of N,N-bis(hydroxyethyl) amines. More
preferably, the salt molecules are N,N-bis(hydroxyethyl)
alkenyl amines quaternized with dialkyl sulfates wherein
the dialkyl sulfates are either dlmethyl- or diethyl
309
sulfate or mixtures thereof, and wherein a major per-
centage, by weight, of the aforementioned salt molecules
comprising the antistatic agent have alkenyl groups
having at least 18 carbon atoms. Preferably the alkenyl
groups may vary in length from about 18 to about 22 carbon
atoms. The alkenyl groups may be either mono- or poly-
olefinically unsaturated, provided that the alkenyl
groups have an average of at least 1.5 olefinic double
bonds per chain.
The preferred antistatic agents of this inven-
tion can also be illustrated by reference to the following
equation and general structural formulae
2 4 H)2 + R 2S04----~[R'N(C2H40H)2R"]+R"SO ~
I II III -
amine quaternizing agent antistatic agent
wherein R' represents an alkenyl group having 18-22
carbon atoms in the chain and being free of substituents
other than hydrogen and free of aromatic groups and hetero
atoms in the chain, and wherein R" is methyl or ethyl.
These quaternary ammonium salt antistatic agents
(III) are obtained by preparing the alkenyl diethanol
amine (I) and quaternizing the amine with dimethyl- or
diethylsulfate quaternizing agent (II).
The alkenyl diethanolamines (I) are readily
available commercially and can be prepared by ~ethods
generally described in the patent literature such as in
U.S. Patent 3,371,130 issued ~ebruary 27, 1968. ~or
example, the amines can be prepared by hydrogenation of the
corresponding amide or nitrile followed by reaction of the
primary amine product with two moles of ethylene oxide.
110~309
The alkenyl diethanolamines can be quaternized
by a quaternizing agent such as dimethyl- or diethyl-
sulfate. For example, the alkenyl dlethanolamine (I) can
be dissolved in a solvent, such as ethyl acetate, the
quaternizing agent (II) added and reacted, followed by
the addition of water, and the removal of the ethyl
acetate via azeotropic distillation to provide the
quaternary antistatic agent (III).
The advantageous characteristics of the
quaternary amine salts of the present invention are
primarily determined by the nature of the alkenyl group of
the salt. Accordingly, the characteristics are largely
dependent on the particular fatty acid from which the
; alkenyl group is derived. It has been found that alkenyl
groups derived from naturally occurring fatty acids
provide particularly desirable properties. Naturally
- occurring animal and vegetable oils comprise mixtures of
fatty acids which vary in chain length, molecular weight
distribution and degree of unsaturation, depending on the
animal or vegetable source from which they are derived.
For example, see Noller, C. R., "Chemistry of Organic
Compounds," W.B. Saunders Company, N.Y. (1957), p. 181,
for an analysis of various animal and vegetable oils.
Fatty acid mixtures derived from vegetable oils,
e.g. cotton, soybean and sunflower oils, are characterized
by a major percentage, by weight, of alkenyl groups, e.g.
60-90% or more, having a 17 carbon chain and wherein almost
all have 1, and 50% or more have 2, olefinic double bonds,
i.e., the alkenyl groups have an average of at least 1.5
olefinic double bonds per chain. Fatty acids from
1104;~09
marine derived oils also have a majority of alkenyl
groups having 1'7-21 carbon atoms with a similarly high
degree of unsaturatiorl. Alkenyl groups f'rom these
sources are characteristically f'ree Or substituents other
than hydrogen on the chain.
A particularly desirable source of alkenyl
groups for use in preparing the amines of the present
invention is soybean oil fatty acids which comprise about
21-29% oleic acid and 50-59% linoleic acid. Soybean oil
is readily available commercially and has been found to
provide antistatic agents with excellent performance
characteristics.
As shown in Table I hereinafter, the above-
described range of chain length and level of unsaturation
appears necessary to obtain the desired balance of carpet
performance properties from the antistatic agents
described herein. The superior performance of amine salts
containing the recited alkenyl groups is particularly
surprising in view of the relatively poor performance of
antistatic agents derived from closely related tertiary
and quaternary amine salts.
The liquid, fluorochemical soil-resistant carpet
treating compositions which are used in combination with
the antistatic agents of the present invention are well
known in the art. These materials comprise mixtures of
fluorinated and non-fluorinated components and can be used
to provide carpets, particularly those having a synthetic
pile fabric, with coatings having excellent soil resistance.
A large number of fluoroaliphatic radical-containing
components is suitable for use in these carpet-treating
~lQ43~3
composltions, both polymeric and non-polymerlc. 'L'hese
components must be non-tacky a.nd non-rubbery solids at
room temperature (e.g. 20-25 C.) and must be both water
and oil repellent in order to prevent soiling, especially
from particulate soil..
I'he fluoroaliphatic component contains a
fluoroaliphatic radical o~ at least three carbon atoms
and generally has at least one major transition tempera-
ture above about 40 C. Transitions are characteristic-
ally glass temperature (Tg) or crystalline melting
points (Tm), such as are usually detected by DTA
(differential thermal analysis) or thermomechanical
~; analysis (TMA). While suitable materials may have, for
-~ example, glass transitions at relatively low temperatures
such as -25 C. to 0 C., the fluorochemical component
generally has at least one major transition temperature
above about 40 C., although materials having a major
transition temperature below 40 C., such as materials
which are waxy or semi-solid, can be useful.
Polymeric fluorinated components can be
addition or condensation polymers, including copol.ymers,
obtained by polymerizing, either a.lone or in conjunction
with compatible monomers free of fluoroaliphatic radicals,
one or more monomers of the formula RfP where Rf is a
fluorinated aliphatic radical and P is a polymerizable
group. Preferably P is an ethylenically unsaturated
moiety polymerizable, or copolymerizable, by free radical
initiation, electron irradiation, ionic initiation, or the
like. RfP may also be a fluoroaliphatic radical~
contai.ni.ng dicarboxylic a.cid, glycol, diamine,
11043~
hydroxyamine, etc., copolymerizable with a diisocyanate,
glycol, diacyl halide, etc. Fluorinated copolymers may
be random, alterrlatirlg, or segmented.
Generally, the fluorinated compounds used in
the invention should contain at least 25 per cent by weight
of fluorine in the form of fluoroaliphatic radicals. A
molecular weight of at least about 20,000 daltons generally
is preferred for the polymers and copolymers to provide
durable non-tacky surface characteristics, although
crystalline polymers with molecular weights as low as
3,000 daltons are useful.
Non-polymeric fluoroaliphatic radical containing
compounds of substantially lower molecular weight such as
urethane compounds(such as described by Guenther and
15 LaZerte, U.S. Patent No. 3,398,182 and U.S. Patent No.
3,484,281); ester compounds (such as described by Dettre
and Greenwood, U.S. Patent No. 3,923,715); carbodiimide
compounds (such as described by Landucci, U.S. Patent No.
3,896,251); and the like, are also useful in this invention.
The fluorinated aliphatic radical Rf is a
fluorinated, preferably saturated, monovalent, non-aromatic,
aliphatic radical of at least three carbon atoms. The
chain may be straight, branches, or if sufficiently large,
cyclic, and may be interrupted by divalent oxygen atoms or
25 trivalent nitrogen atoms bonded only to carbon atoms. A
fully fluorinated group is preferred, but hydrogen or
chlorine atoms may be present as substituents in the
fluorinated aliphatic radical provided that not more than
one atom of either is present in the radical for every two
- 30 carbon atoms, and that the radical must at least contain a
110430~
-- 8 --
terminal perfluoromethyl group. "Terminal" as used herein
refers to the position in the skeletal chain of the
radical furthest removed from the linkage which connects
the Rf radical with the body of the molecule. Preferably,
the fluorinated aliphatic radical contains not more than
20 carbon atoms because such a large radical results in
inefficient use of the fluorine content.
Representative fluorinated components, and
reactants for preparin~ these components, are descrlbed in
the patent literature such as in U.S. Patent 3,916,053,
issued October 28, 1975, particularly at Column 4, line 5,
through Column 5, line ~0; U.S. Patent 3,896,035 issued
July 22, 1975, particularly at Columns 3 and 4, and U.S.
Patent 3,923,715 issued December 2, 1975, particularly at
Table I.
As noted previously, the fluorochemical, soil-
resistant, carpet treating compositions comprise a second
polymeric component in addition to the fluoraliphatic
component. Such compositions provide a normally solid,
soil-resistant coating comprising (a) at least one phase
of a water-insoluble addition polymer derived from a poly-
merizable, ethylenically unsaturated monomer free of non-
vinylic fluorine and having at least one major transition
temperature above about 40C. and a solubility parameter of
at least about 8.5 and (b) at least one phase of a water-
insoluble fluorinated component as described hereinabove
wherein at least one of the phases is a continuous phase.
The ratio of fluorinated component to addition polymer is
preferably in the ratio, based on weight, of from about
. 30
k~
~10430~
1:10 to 10:1, provided that the mixture contains at least
5 percent by weight of fluorine in the form of fluoro-
aliphatic radicals.
The water-insoluble addition polymers useful in
these two-phase carpet treating compositions can be
characterized as being normally non-rubbery or curable to
a non-rubbery state, non-tacky, normally solid, water-
insoluble, and preferably free of ethylenic or aeetylenic
unsaturation. Water insolubility is required to provide
durability to the normal cleaning operations, such as
shampooing. In order to be resistant to soil under high
compressive load, especially particulate soil, the
addition polymer must have at least one major transition
temperature above about 40 C., which is a melting point
or glass transition at which the polymer becomes
significantly softer as the temperature is raised.
The addition polymers may be prepared from
suitable monomers sueh as vinyl fluoride, vinylidene
fluoride, vinyl ehloride, vinylidene chloride, styrene,
alpha-methyl styrene, lower alkyl methacrylates, and
glycidyl acrylate and methaerylate. Such monomers can be
polymerized or copolymerized wîth each other or with minor
amounts, e.g. 0.5 to ~5% of additional monomers to provide
or improve particular desired physical or chemical
properties, e.g. flexibility, substantivity, surface
conductivity, etc. Representative of sueh additional
monomers are vinyl acetate, vinyl pyridine, alkyl acrylates
or methacrylates, hydroxy lower alkyl acrylates and
methacrylates, acrylamide and methacrylamide, N methylol
acrylamide, itaconic acid and maleic anhydride. The
~104309
-- 10 --
amounts of such additional monomer used must of course
not be so great as to impart water solubility to the
addition polymer. Also, at least one major transition
temperature of the addition polymer must remain above
about 40 C. Polymerization may be accomplished in bulk,
solution, suspension or emulsion systems by any of the
usual polymerization agents, such as gamma radiation,
actinic radiation, organic or inorganic peroxides,
azobisalkylnitriles, anionic or cationic agents, and the
like.
Representative two-phase carpet treating
compositions and processes particularly useful in the
practice of the present invention are described in the
patent literature, such as in U.S. Patent 3,916,053,
issued October 28, 1975 (Example IX), and U.S. Patent
3,923,715, issued December 2~ 1975 (Example 9). Other
two-phase carpet treating compositions comprising
fluorinated and fluoroaliphatic radical-free urethane
adducts are useful in the present invention. Compositions
of this type are described in U.S. Patent 3,896,035,
issued July 22, 1975.
. Carpets and rugs can be treated with the composi-
tions of this invention by any of the customary precedures,
such as by padding, spraying, roll-coating and the like.
Application by top-spraying a dyed carpet pre-wet to about
40 to 100 percent face pile weight is preferred. The
treating composition can be applied from aqueous or non-
aqueous solutions or suspensions and the antistatic agent
and the fluorochemical, soil-resistant carpet-treating
~104309
composition can be coapplied or applied sequentially.
The most convenient and generally most economical
procedure is to prepare a treating solution by blending
appropriate quantities of the antistatic agent with the
fluorochemical, soil-resistant carpet treating composition.
Most preferably, an aqueous solution comprising, for
example, about 20% solids by weight of the antistatic
agent is blended with an aqueous solution suspension or
emulsion, generally a cationic emulsion, comprising about
45% by weight soil-resistant carpet treating solids,
diluted with water. Other conventional adjuvants compat-
ible with the above-described components, such as
softeners, wetting agents,.and the like, may be present.
The ratio of the antistatic agent to the fluoro-
chemical-containing treating composition, based on weight
of the solids, can vary from about 1:10 to about 1:1 and
is most preferably in the range of about 1:3 to 2:3. The
actual concentration of treating solids in the liquid
treating solution or emulsion will depend on the amount of
liquid to be applied during treatment. This will, in turn,
depend on the construction and composition of the carpet
as well as the application and drying facilities which are
used. Generally a total application of antistatic agent
equal to about 0.01 to about 1 percent of the face pile
weight of the carpet is required and should be contained
in an amount of water corresponding to about 3 to 150,
preferably 10 to 30, percent of the face pile dry weight.
Thus, aqueous treating solutions containing from about 0.3
to about 1.5 weight percent treating solids are preferred
and most preferably the treating solids should comprise
11(J4309
about 0.5 to 3 weight percent of the aqueous treating
solution.
When the carpet treatment is to be applied at
the dyehouse, the most convenient method is to spray the
solutions on to the carpet surface after the dyeing
operation and prior to the drying oven. When treatment
is to be applied as part of the backing step, the carpet
can be sprayed as part of the laminating operation, to
be followed by oven drying.
The advantages of treating carpets, particularly
low denier nylon fiber face pile carpets, with the
treating compositions of the present invention is shown
in the example which follows wherein carpets have been
treated with the compositions of this invention and the
treated carpets evaluated to determine the performance
properties of the carpets. More specifically, tests of
treated carpets were conducted to determine the static
propensity, oil and water stain repellency, soil resis-
tance, hand and luster.
The test for static propensity is conducted by
- having a subject walk on a carpet under standard condi-
tions using standard test shoes. The build-up of static
charge on the subject is then measured on an electrometer.
The test is conducted at 21 C. and 20% relative humidity
25 in accordance with AATCC Test Method 134 - 1975, except
that testing was done on two consecutive days, the total
stepping time for each test was 30 seconds and a rubber
pad was used under the carpet. Shoes havlng both neoprene
~- "Neolite" (a trade name of Goodyear Tire and Rubber
Company) and chrome tanned leather soles and heels were
Tf~d~ ~nGrk
- 12 -
110~30~
used in the tests. It has been found that a generated
static charge of about six kilovolts or more will produce
discomfort. Generally if the potential is below about
3 kilovolts, no signif'icant effect is observed.
Stain repellency is evaluated in accordance
with standard procedures. Oil repellency is tested in
accordance with AATCC Test Method 118 - 1966T, Hydrocarbon
~esistance Test, in which the higher the number, the
greater the resistance to staining by oils. A value of 3
or greater indicates satisfactory performance. Carpets
without an effective fluorochemical treatment will
generally score zero in this test.
Resistance to water-borne stains is evaluated by
placing isolated drops of 70:30 or 80:20 isopropanol:water
on the carpet pile surface at 25 C. If the drop fails to
penetrate the surface and wet the fiber within 10 seconds,
the treatment is considered effective.
Soil resistance is evaluated in accordance with
AATCC Test Method 122 - 1967T, a walk-on test. This is a
comparative test, each sample consisting of a test piece
30 by 15 cm and a control piece 30 by 15 cm. The combina-
tion is placed side by side in a heavily travelled
industrial area for an exposure of about 12,000 steps at
about 25 C. and 50 - 70% relative humidity. The samples
are rotated periodically to insure uniform exposure and
are vacuumed every 24 hours during the test and before
visual evaluation.
In this test the control was a carpet which had
been treated only with the fluorochemical soil-resistant
composition prepared as described in Part A of' the following
- 13 -
ilO4~09
example. Test carpets were then treated with the same
soil resistant composition plus antistatic agent;.
The control was tested and assigned a soil
resistance value of zero. The test carpets were
similarly exposed to soiling conditions and assigned a
rating on a scale of 0 to -9 in comparison to the control
wherein negative numbers represent increasirlgly greater
soiling.
The "hand" and "luster" tests are subjective
tactile and visual tests conducted by an experienced
evaluator. Hand relates to the softness of the carpet
pile surface experienced when the open palm of a human
hand is rubbed across the pile face. The carpet under
test is assigned a value ranging from 1 to 5. (The values
used in obtaining the results reported in Table I are an
- average of readings by three different evaluators.) The
value obtained is compared to the value for a specified
control sample which was treated with the same soil
resistant composition as the test carpet, but without the
antistatic agent. The results were reported in Table I as
"better than" (+%) or "worse than" (-%) the control value.
These percentages are obtained by subtracting the value for
the control from the value for the test carpet and dividing
this difference by the control value.
Because the hand of a carpet is sensitive to
changes in relative humidity, the carpet is tested
initially when removed from the dryer (about 15% R.H.) and
also following conditioning at 50% R.~. for 24 hours at
room temperature.
- 14 -
1~0430~
].uster is also a subjective test by which a
ratin~ is assigned to the carpet on a sca]e of :L to 5
(again, the average of` readings by three evaluators is
used~. The rating is compared to the rating obtained by
a control carpet and the results reported as "better than"
(~%) or "worse than" (-%) the control carpet with percent-
age values being calculated as for the "hand" test and
reported in Table I.
As performed, the hand and luster tests provide
a measure of the effect of adding the antistatic agent to
the carpet treatment. Ideally the agent should not
adversely affect the carpet properties while at the same
time improving the static potential property of the carpet.
In order to exemplify the present invention, a
soil resistant treating composition and an antistatic agent
were prepared.
A: Soil Resistant Co position
A soil resistant carpet treating composition was .
prepared comprising a fluoroaliphatic radical-containing
component and a fluorine-free acry]ate copolymer.
A his-urethane fluc,roaliphatic radical-
containing component for carpet treatment was prepared
according to Example IX of U.S. ~atent 3,~16,053, issued
October 28, 1975, from 554 par~s of N-ethyl perfluoro-
octanesulfonamidoethanol. A solution of this alcohol in337 parts of methyl isobutyl ketone was dried of water by
distilling to remove 100 parts of solvent and was then
cooled to 80 C. To this solution was added 81 parts of
tolylene diisocyanate and then very slowly 0.32 part:s of
dibutyl tin dilaurate as the exothermic reaction permitted.
- 15 -
110430~
The reverse procedllre of adding the catalyst f:lrst and
the diisocyarlate gradually is also satisfactory. A~ter
reaction~ an emulsioll was prepared in a dispersion of
489 parts of water containinK a solution of 16 parts o~
fluoroaliphatic surfactant,
C8F17S2NHC3~6N (CH3)3Cl
in 16 parts acetone and 48 parts water and 16 parts of
polyoxyethylene sorbitan monooleate by putting the total
dispersion through an homogenizer at 2500 pounds per square
inch and 75 C. The emulsion had a solids content of 45%.
The solid material had a melting point of 110 - 125 C.
An acrylate copolymer was prepared by adding to
a glass-lined reactor 3780 parts by weight of water, 108
parts of a polyethoxylated stearyl ammonium chloride
cationic surfactant, and 4 parts reactive cationic monomer
having the formula
CH2 = C(CH3) CO2CH2CH(OH)CH2N (CH3)3Cl
The solution was freed of oxygen by alternately evacuating
and repressuring with nitrogen. 720 parts of methyl-
- 20 methacrylate and 720 parts of ethylmethacrylate were then
added, the mixture heated to 60 C., and 14 parts of a
free radical polymerization initiator (2,2'diguanyl
-2,2'azaprcpane hydrochloride), dissolved in water, was
added. When the reaction was initiated and the tempera-
ture began to rise, the temperature was maintained at 85C.
while a mixture of 2880 parts methylmethacrylate, 2380
parts ethylmethacrylate, and 4200 parts of water was
slowly added. Agitation at 85 C. was continued until
completion, about six hours. The acrylate copolymer
- 16 -
11043~9
emulsion contained about 45% copolymer solids.
A stain and soi1-resistant carpet treating
composition was prepared by blending 1 part of the
fluoroaliphatic radical-contalning bis-urethane emulsion
with 2 parts of the acrylate copolymer emu]sion.
B: Antistatic Agent
An antistatic agent was prepared by dissolving
350 parts N,N-bis(hydroxyethy]) soya amine ("Ethomeen*
S/12, Armour Chemical Co.) in ethyl acetate. The solution
was heated to 60 C. and 14LI.8 parts of diethyl sulfate
was added. The mixture was heated at 60 C. for one hour,
followed by the addition ol' water and the removal of the
ethyl acetate by azeotropic distillation. A 20% solids
aqueous solution was obtained.
Carpet samples were treated with the soil-
resistant composition described in A above to provide
control samples. An antistatic carpet-treating composition
comprising 45 parts by weight of composition A and 33
parts of antistatic agent ~ was prepared by mixing with
20 922 parts water. Carpet samples prewet to 75% wet pickup
were treated with this antistatic composition at the rate
of 0.32% total solids on dry face pile weight, then tested
and compared with the control. The results are shown in
Table I hereinafter.
To further demonstrate the uniqueness of the
antistatic agents of the present invention, Table I shows
antistatic agents comprising quaternary and tertiary amine
salts of similar amine compounds cornpared with those of the
present invention.
~r~de ~k
- 17 -
110~309
In Table I, the antistatic agent of the present
invention prepared in "B" above (N-ethyl N,N-bis(hydroxy-
ethyl) soya ammonium ethylsulfate) will be identified as
antistatic agent "1". The antistatic agents compared
with agent 1 of the present invention will be identified
- in Table I according to the following schedule:
2. N,N-bis(hydroxyethyl) soya ammonium hydrogen
sulfate
3. N,N-bis(hydroxyethyl) soya ammonium acetate
4. N,N-bis(hydroxyethyl) soya amine (free base)
5. N-ethyl-N-8-hydroxy-3,6 dioxooctyl-N-5 hydroxy-3-
oxopentyl soya ammonium ethyl sulfate
6. N-ethyl -N,N-bis(hydroxyethyl) oley ammonium
ethyl sul~ate
7. N-methyl-N,N-bis(hydroxyethyl) coco ammonium
chloride
8. N-methyl-N,N-bis(hydroxyethyl) stearyl ammonium
chloride
9. Methyl tris(hydroxyethyl) ammonium sulfate
10. Hydroxyethyl trimethyl ammonium sulfate.
- The "Soil-Resistant Composition" referred to in
Table I is the composition "A" described hereinabove,
unless noted otherwise.
- 18 -
1104309
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- 19 -
